JP3032882B2 - Polyurethane resin-forming composition for sealing material of membrane module - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a castable polyurethane resin-forming composition, and more particularly to a castable polyurethane resin-forming composition suitable for use as a sealing material for membrane modules used in blood treatment devices, water purifiers and the like. About things.

[0002]

2. Description of the Related Art As a polyurethane resin-forming composition comprising a main component comprising a polyisocyanate component and a curing agent comprising a polyol component for the purpose of sealing a membrane module, an aromatic polyisocyanate and a castor oil-based polyol have conventionally been used. And a sealing material comprising a tertiary amino group-containing polyol (for example, JP-A-53-9).
No. 8398). However, when these sealing materials are used, there is a problem that the amount of eluted substances from the sealing portion is large. For the purpose of improving this, a product using a prepolymer of hexamethylene diisocyanate as a polyisocyanate component (for example, JP-A-60-58156)
Japanese Patent Application Laid-Open No. 62-13620), and those using a bullet-modified hexamethylene diisocyanate.
No. 8), using a modified trifunctional isocyanurate of hexamethylene diisocyanate (see, for example,
No. 215822) has been proposed.

[0003]

[Problems to be Solved by the Invention] Hemodialysis has been performed for several years to 10 years.
As the age increases, amyloidosis due to accumulation of β2-microglobulin, hyperlipidemia due to lipid metabolism disorders, and the like are observed. Therefore, in order to remove these medium molecular weight substances, a dialyzer having a large filtration area using a hollow fiber having a large surface area is used. If the viscosity of the sealing material is high because the hollow fiber used is thin, there is a problem that the hollow fiber is deformed or broken at the time of injecting the sealing material, thereby lowering the filtration performance of the dialyzer. Therefore, the viscosity of the mixture of the main agent and the curing agent during molding is 1,500 mPa · S /
Those having a temperature of 25 ° C. or less are demanded.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by using a specific modified polyisocyanate, the composition of a sealing material having a low viscosity, good molding workability and a small amount of elution can be obtained. I found something and arrived at the present invention.

That is, the present invention relates to a polyurethane resin-forming composition comprising a main component comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B), wherein the above (A) comprises (i) uretdione dimer Body (a1)
(A) or a modified polymer of hexamethylene diisocyanate containing as a main component, or a prepolymer of (a) and a polyol, and (ii) a prepolymer of diphenylmethane diisocyanate and a polyol or carbodiimide-modified diphenylmethane diisocyanate. A polyurethane resin-forming composition for a sealing material of a membrane module, and a polyurethane resin-forming composition comprising a main agent comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B). ) Is a modified form of hexamethylene diisocyanate (a) containing uretdione dimer (a1) as a main component, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, A sealing material for a polyurethane resin forming composition of the membrane module, characterized by comprising the aromatic polyisocyanate compound selected from the prepolymer from the.

Hexamethylene diisocyanate (hereinafter abbreviated as HDI) constituting the polyisocyanate component (A)
Examples of the modified (a) include those obtained by reacting HDI in the presence of a catalyst or those obtained by reacting HDI and an alcohol in the presence of a catalyst. As the catalyst, triethylphosphine, dibutylethylphosphine, tri-
Isobutylphosphine, tri-n-butylphosphine,
Trioctyl phosphine, tribenzyl phosphine and the like can be mentioned. The reaction is usually carried out at a temperature of 50 to 100 ° C., at the stage of the target reaction rate, the reaction is stopped by adding phosphoric acid or the like, and the unreacted HDI is removed under a high vacuum of 0.1 Torr or less.
Remove by thin-film distillation at 120 ° C. or higher, or extract with n-hexane. Modified form of HDI in the present invention (a)
The amount of the modified uretdione derivative of HDI (a1) is usually 40% by weight or more, preferably 50% by weight or more. When the content of (a1) is less than 40% by weight, the effect of lowering the viscosity becomes insufficient even when the modified HDI of the present invention is used. Specific examples of (a) include "Duranate X-1424" manufactured by Asahi Kasei and "Sumidur N-3400" manufactured by Sumitomo Bayer Urethane.

The isocyanate component (A) in the present invention
, A combination of the following (1) or (2) is used. (1) Modified (a) of hexamethylene dissocyanate (HDI) containing uretdione dimer (a1) as a main component or a prepolymer of (a) and a polyol, and diphenylmethane diisocyanate (MD)
A combination of a prepolymer or carbodiimide-modified MDI from I) and a polyol. Examples of the polyol used for the prepolymer of (a1) and the polyol include those described in JP-A-63-246175.

(2) Modified HDA (a) containing uretdione dimer (a1) as a main component, and aromatic polyisocyanate compounds selected from MDI, carbodiimide-modified and prepolymers of these and polyols combination. Such polyols include, for example, those described in
-246175.

The content of isocyanate groups (NCO groups) in the polyisocyanate component (A) is usually 10 to 25% by weight, preferably 12 to 23% by weight. If the amount is less than 10% by weight, the curing speed will be low, and if it exceeds 25% by weight, the hardness of the cured resin will be too high and the workability after curing, for example, the cutting property will be reduced.

The polyol component (B) is disclosed in
-58156 Polyether polyols, castor oil-based polyols (such as castor oil), mixtures of polyester polyols and the like with tertiary amino group-containing polyols, and castor oil and tertiary amino group-containing polyols as described in JP-A-58156 And a reaction product obtained by transesterification reaction with

Examples of the tertiary amino group-containing polyols include triethanolamine, alkylene oxide adducts of alkylenediamine (such as ethylene oxide and propylene oxide), and polyalkylene polyamine adducts of alkylene oxide. Of these, preferred are alkylene diamines and alkylene oxide adducts of polyalkylene polyamines, and particularly preferred are N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and N, N,
N ', N', N "-pentakis (2-hydroxypropyl) diethylenetriamine.

Particularly preferred as the polyol component (B) in the present invention is a mixture of castor oil and / or a trimethylolpropane ester of castor oil fatty acid and a tertiary amino group-containing polyol. The hydroxyl value of the polyol component (B) is usually 150 to 800, preferably 2
00 to 600.

In the composition of the present invention, the NCO / OH equivalent ratio when the main component (A) and the curing agent (B) are mixed and cast is usually 0.5 to 2.0, Preferably it is 0.8 to 1.5. If the corresponding amount ratio is less than 0.5, the hardness of the cured product becomes insufficient, and if it exceeds 2.0, the amount of eluted material in the cured product increases, which is not preferable.

The gelation time when the composition of the present invention is cast at room temperature is usually 5 to 60 minutes, and the time until the hardness reaches 90% of the ultimate hardness is usually 24 hours at room temperature. It takes up to 72 hours, but the curing temperature is high (30-60
C), the time can be further reduced.

The component (A) in the present invention is stable even when stored at a low temperature of 10 ° C. or lower and does not change its properties even when a heat cycle of 45 ° C./0° C. is repeated. Can be stored for a period. In addition, since the amount of eluted material after casting and curing is extremely small, blood processing equipment (hollow fiber type, membrane type or coil type artificial kidney, plasma separation module, etc.), artificial organs (artificial lung, etc.), water purifiers, It is suitable as a sealing material for membrane modules such as ultrafiltration membranes (hollow fiber type, spiral type, etc.).

The method of using the composition of the present invention is not particularly limited, but an example of use in the case of using it for a blood processor is shown below. First, a main agent composed of the component (A) and a curing agent composed of the component (B) are separately prepared in advance.
Each is defoamed under reduced pressure (for example, 20 mmHg × 2 hours). Next, the main agent and the curing agent are weighed and mixed so as to have a predetermined NCO / OH equivalent ratio. The hollow fiber is embedded in a container (comprising polycarbonate resin, acrylonitrile-styrene resin, acrylonitrile-styrene-butadiene resin, etc.) by centrifugal casting (molding) using the mixed solution. An example of the centrifugal casting (molding) method is described in JP-B-57-58963.
This is described in the specification of Japanese Patent Publication No. As the hollow fibers to be embedded, generally, hollow fibers such as cellulose, acrylic, polyvinyl alcohol, polyamide, and polysulfone containing 5 to 80% by weight of glycerin are used. The mixture gels 5 to 60 minutes after injection,
The module can be removed from the casting (molding) machine. Curing is performed at 40 ° C. for about 2 days to complete the curing.
Then, it is usually 30 ° C. at 121 ° C. using an autoclave.
The product is sterilized by steam heating for a minute. Sterilization can also be performed by a method other than steam, such as ethylene oxide gas treatment or γ-ray irradiation.

The polyurethane resin obtained by curing the composition of the present invention has very good adhesion to the hollow fiber, and the amount of the eluate from the polyurethane resin and the hollow fiber bonding portion is small. In addition, when used for a water purifier due to high hardness, a product having good hot water resistance can be obtained.

[0018]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
In the following, "%" indicates% by weight.

[0019]

【Example】

Example 1 A 2 L volume 4 equipped with a stirrer, thermometer and nitrogen inlet tube
351.9 g of MDI (“Millionate MT” manufactured by Nippon Polyurethane) and 148.1 g of castor oil (“ELA-DR” manufactured by Toyokuni Oil) were charged into a one-necked flask, and heated to 70 to 80 ° C. while stirring under a nitrogen stream. After reacting for hours,
Modified product containing uretdione dimer (“Duranate X-1424” manufactured by Asahi Kasei: containing 55% of uretdione dimer) 5
00.0 g was charged, and the mixture was stirred at 45 ° C. for 30 minutes and uniformly mixed. The NCO content of the obtained product was 21.5%. This is designated as the main agent (A-1).

In a reaction vessel similar to the one prepared in (A-1), 250.0 g of pentakishydroxypropyldiethylenetriamine and 750.0 g of castor oil were charged.
The mixture was stirred at 40-50 ° C. for about 30 minutes and mixed uniformly. This had a hydroxyl value of 312. This is referred to as a curing agent (B-1).

A hollow fiber containing 60% by weight of glycerin was inserted into a polycarbonate container, and (A-1) and (B-1) were mixed at an NCO / OH equivalent ratio of 1.05 / 1.0.
The mixture was stirred and mixed for 10 seconds, and then centrifugally cast (molded). After curing at 40 ° C. for 2 days, blood circuit connecting parts were attached to prepare an artificial kidney module. Thereafter, the module is irradiated with gamma rays (2.5 Mrad
Irradiation) and sterilized. Tables 1 and 2 show the performance test results.

Comparative Example 1 351.9 g of MDI and 148.1 g of castor oil were charged into a reaction vessel similar to the one prepared in Example 1 (A-1), and heated to 70 to 80 ° C. while stirring under a nitrogen stream. Shi 4
After reacting for an hour, HDI having an average number of isocyanate groups of 3
Isocyanurate modified product (Duranate T manufactured by Asahi Kasei Corporation)
PA-100 ": uretdione dimer 1% or less) 50
0.0 g was charged and stirred at 45 ° C. for 30 minutes to mix uniformly. The NCO content of the obtained product was 21.5%.
This is designated as Comparative Main Agent (A-2). (A-2)
A module was prepared in the same manner as in Example 1, except that the module and the curing agent (B-1) of Example 1 were used. The performance test results are shown in Tables 1 and 2.

Comparative Example 2 A reaction vessel similar to the one prepared in Example 1 (A-1) was charged with 351.9 g of MDI and 148.1 g of castor oil, and heated to 70 to 80 ° C. while stirring under a nitrogen stream. After heating and reacting for 4 hours, 500.0 g of a modified burette of HDI (“Duranate 24A-100” manufactured by Asahi Kasei) was charged, and the mixture was stirred at 45 ° C. for 30 minutes and uniformly mixed. The NCO content of the product obtained was 21.6%. This is designated as Comparative Main Agent (A-3). Using (A-3) and the curing agent (B-1) of Example 1, a module was prepared in the same manner as in Example 1. Table 1 and Table 2 show the performance test results.
Shown in

Comparative Example 3 M was added to a reaction vessel similar to the one prepared in (A-1).
703.8 g of DI and 296.2 g of castor oil were charged and heated to 70 to 80 ° C. with stirring under a nitrogen stream to react for 4 hours. The NCO content of the obtained product was 20.0%. This is designated as Comparative Main Agent (A-4). The (A-
Using 4) and (B-1) of Example 1, a module was created in the same manner as Example 1. Table 1 shows the performance test results.
And Table 2.

[0025]

[Table 1]

The test method is as follows. Initial mixing viscosity: The viscosity of the mixture of the main agent and the curing agent at 25 ° C. one minute after the start of mixing. Gelation time: Indicates the time until the viscosity of the mixed solution reaches 10,000 mPa · s after mixing. Hollow fiber state after casting: The state of the hollow fiber in the portion sealed with the resin after casting was visually determined. Elution amount: Module 1 cured and cured at 40 ° C for 2 days
The hollow fiber-bonded portion is cut out and cut into 1 cm square.
To this, 200 ml of deionized water is added, and the mixture is extracted with gentle shaking at 40 ° C. for 2 hours. After cooling, take 1.0 ml of the supernatant and add deionized water to make exactly 50 ml. This solution was used as a test solution, and deionized water was used as a control.
The absorbance at 0-240 nm is measured. (The dissolution test method specified in the dialysis type artificial kidney device approval standard [Notice No. 494 of the Director of Pharmaceutical Affairs Bureau, Ministry of Health and Welfare])

[0027]

[Table 2]

The test method is as follows. Storage stability: The main agent is stored in a 10 ° C. constant temperature bath for one month, and changes in appearance are observed. Heat cycle test: 4 main ingredients
Store at 5 ° C for 12 hours and then at 0 ° C for 12 hours to make one cycle. After repeating this for 20 cycles,
Observe changes in appearance.

[0029]

The polyurethane resin-forming composition for a sealing material of a membrane module according to the present invention has the following effects. (1) The viscosity of the sealing material is low, and the moldability is good. (2) Since the amount of eluted material after casting and curing is extremely small, when used as a sealing material for a membrane module used for blood treatment or the like, the amount of eluted material eluted into the blood from the sealing material is small and high safety. (3) Since it is excellent in stability at low temperatures and heat cycle resistance, it can be stored for a long time even in winter. Due to the above effects, the composition of the present invention can be used for a blood processor (hollow fiber type, membrane type or coil type, artificial kidney, plasma separation module, etc.), artificial organ (artificial lung, etc.), water purifier, It is extremely useful as a sealing material for membrane modules such as ultrafiltration membranes (hollow fiber type, spiral type, etc.).

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) A61M 1/14-1/26 B01D 63/00 C08G 18/63-18/79 C09K 3/10 C09D 175 / 04 WPI / L (QUESTEL)

Claims (3)

(57) [Claims] 1. A polyurethane resin-forming composition comprising a main component comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B), wherein said (A)
Is (i) a modified product of hexamethylene diisocyanate (a) containing uretdione dimer (a1) as a main component or a prepolymer of (a) and a polyol, and (ii) a prepolymer of diphenylmethane diisocyanate and a polyol. A polyurethane resin-forming composition for a sealing material of a membrane module, comprising a prepolymer or carbodiimide-modified diphenylmethane diisocyanate. 2. A polyurethane resin-forming composition comprising a main agent comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B), wherein said (A)
Is a modified form of hexamethylene diisocyanate (a) containing uretdione dimer (a1) as a main component, and an aromatic polyisocyanate compound selected from diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and a prepolymer of these and a polyol. A polyurethane resin-forming composition for a sealing material of a membrane module, comprising: 3. The uretdione dimer (a1) content in the modified hexamethylene diisocyanate (a) is 4%.
3. The composition according to claim 1, which is 0% by weight or more.